Graft copolymers comprised of certain monomeric vinyl benzyl polyglycol ethers on nu-vinyl-3-morpholinone polymer substrates and improved acrylonitrile polymer compositions obtainable therewith



June 18, 1963 s A. MURDOCK 3,0 ,5 5

GRAFT COPOLYMERS COMPRISED OF CERTAIN MONOMERIC VINYL BENZYL POLYGLYCOL ETHERS ON N-VINYL-IE-MORPHOLINONE POLYMER SUBSTRATES AND IMPROVED ACRYLONITRILE POLYMER COMPOSITIONS OBTAINABLE THEREWITH Filed Sept. 28, 1959 Fi/omen/ous ar/l'c/e comp/vised 0/ an acry/on/b rfle ,oo mer having a graf/ copo/yme/ 0/ a monomer/c why/bergy/poQy/yca/ 61% er /014 copo/ mer/ ea upon on /V- why/-3-mor,o o/fnone ,oo /y m er Jabs r012.

IN V EN TOR. 8/00 A93 19. Murdock 2' 1- CGPOLYMERS COMPRISED F CERTAW MONSMERIC VINYL BENZYL POLYGLYCGL ETHERS 0N N-VlNYL-I'i-MOHOLINONE POLY- MER SUBSTRATES AND RSVED ACRYLO- NITRILE PGLYMER CGMPOSHTIONS OBT- ABLE THEREWKTH Stanley A. Murdock, Rancho tl'ordova, Calif, assignor to The Dow (Zhemical Company, Midland, Mich, a corporation of Delaware Filed Sept. 28, 1959, Ser. No. 842,948 19 Claims. (Cl. 260-455) The present invention resides in the general field of organic chemistry and contributes specifically to the polymer art, especially with respect to certain graft copolymer compositions and fiber-forming polymer blends obtainable therewith. It is particularly concerned With graft copolymers of certain monomeric vinyl benzyl polyglycol ethers that are graft copolymerized upon or with preformed N-vinyl-3-morpholinone polymer substrates (hereinafter referred to as VM polymers), which graft copolymers have especial utility as dye-receptive, antistatic and stabilizing additaments for acrylonitrile polymer compositions which, advantageously, may be of the fiber-forming variety.

The invention is also concerned with the compositions that may be obtained by blending the graft copolymers with acrylonitrile polymers, as well as with shaped articles which have been fabricated from such compositions and which, as a consequence, have significantly enhanced properties and characteristics as regards improvements in and relating to enhanced dyereceptivity, minimized inherent propensity to accumulate electrostatic charges, natural stability to various deteriorating influences, including stability against becoming deleteriously influenced and degraded upon exposure to heat at elevated temperatures and to light.

Within the scope and purview of the invention, there are comprehended (1) the various novel and utile graft copolymers of the indicated variety; (2) the advantageous polymer compositions, particularly fiber-forming compositions, obtained by blending the graft copolymers with acrylonitrile polymers; (3) various shaped articles fabricated from and comprised of the graft copolymeroontaining acrylonitrile polymer compositions; and (4) methods for the preparation of the above-indicated compositions.

It is the main purpose and primary design of the present invention to provide and make available graft copolymers of certain monomeric vinyl benzyl polyglycol ethers upon preformed VM polymer substrates that are especially well suited for being incorporated in acrylo nitrile polymer compositions, particularly compositions of polyacrylonitrile, to serve in the indicated treble capacity of dye-assisting adjuvants, antistatic agents and stabilizing ingredients. It is also a principal aim and chief concern of the invention to provide and make available acrylonitrile polymer compositions and shaped articles therefrom that contain the above-indicated and hereinafter more fully delineated type of graft copolymeric additaments which compositions have, as intrinsic distinguishing characteristics, excellent receptivity of and acceptability for any of a wide variety of dyestuffs; permanently imbued antistatic properties that are unusually good for and not commonly encountered in polymeric materials of the synthetic, essentially hydrophobic varieties of such substances; and efficacious natural stability to heat and light, as well as to certain chemical conditions, such as alkaline environments.

The graft copolymers of the present invention which have the indicated capacity and utility as additaments for acrylonitrile polymer compositions are comprised of a Patented June 18, 1963 ice preformed VM polymer trunk or base upon which there is graft copolymerized certain monomeric vinyl benzyl polyglycol ethers of the variety hereinafter described. Advantageously, the graft copolymers may also be prepared from mixtures of the referred-to monomeric polyglycol ethers with mixtures of certain monomeric, al-

kenyl, particularly vinyl, group-containing organic sulfonic acid compounds or derivatives thereof, also hereinafter more fully delineated.

The polymer blend compositions of the present invention which fulfill the above-indicated ends and offer corollary advantages and benefits, particularly as fiberforming compositions as will hereinafter be manifest, are, in essence, comprised of an intimate and practically inseparable blend, mixture or alloy constitution of (A) an acrylonitrile polymer that contains in the polymer molecule at least about 80 weight percent of acrylonitrile, any balance being copolymerized units of another ethylenically unsaturated monomeric material that is co polymerizable with acrylonitrile to provide fiber-forming acrylonitrile polymer products and, most advantageously, is polyacrylonitrile and (B) a minor proportion of the above-indicated variety of beneficial graft copolymeric additament that functions in the described manner.

The methods of the invention by which the herein contemplated advantageous compositions may be made involve preparation of the graft copolymer, as well as incorporation of a minor proportion of the graft copolymer product as a beneficial additament in and with the acrylonitrile polymer base by any of several beneficial techniques, hereinafter more thoroughly defined, adapted to suitably accomplish the desired result.

Without being limited to or by the specific embodiments and modes of operation set forth, the invention is illustrated in and by the following didactic examples wherein, unless otherwise indicated, all parts and percentages are to be taken on a weight basis.

ILLUSTRATION A Into a 500 ml. reactor that is equipped with an efficient agitator, a nitrogen sparger, and a total reflux condenser, there is charged about 31.5 grams of poly-N- vinyl-3-morpholinone (PVM) having a Fikentscher K- value of about 45; about 7.2 grams of monomeric 1- (Z-methoxyethoxy)-2-(vinylbenzyloxy)ethane; about 6.3 grams of sodium styrene sulfonate; about 0.5 gram of potassium persulfate; and about 181.8 grams of water. The resulting mixture is brought to about pH 6 by acidification with hydrochloric acid (HCI). Under continued nitrogen sparging and with continued stirring, the acidified reaction mass is maintained at a temperature of about 60 C. over a 19 hour period. At the end of this time, the reaction is terminated. About 75.5 percent of the monomers are found to be converted to a graft copolymeric pnoduct which is obtained as white emulsion of the graft copolymer, containing about 20 percent of the water-insoluble graft copolymer solids dispersed in water. Upon analysis, the graft copolymeric product is found to contain about 14 percent of polymerized polyglycol ether monomer units; 11 percent of polymerized sodium styrene sulfonate units; and about percent of 'PVM.

Polyacrylonitrile fibers containing about 10 percent of the above copolymer product are prepared by impregnating filamentary structures that are in aquagel condition (after having been salt-spun and wet-stretched) in and with an aqueous dispersion of the copolymer that contains about 1.5 percent of the graft copolymer solids. The polyacrylonitrile aquagel fiber that is employed is obtained by extruding a spinning solution of fiber-forming polyacrylonitrile comprised of about 10 parts of the polymer dissolved in 90 parts of a 60 percent aqueous solution of zinc chloride through a spinnerette having 750 individual 6 mil diameter orifices into an aqueous coagulating bath that contains about 43 percent of dissolved zinc chloride to form a multiple filament tow. After being spun, the tow bundle of coagulated polyacrylonitrile aquagcl fiber is washed substantially free from salt upon being withdrawn from the coagulating bath and then wetstretched for orientation to a total stretched length that is about thirteen times its original extruded length. The aquagel fiber containing about two parts of water for each part of polymer therein, is then passed through the mentioned aqueous impregnating bath of the dissolved copolymer additive so as to become impregnated therewith to the indicated extent.

Following the impregnation, the aquagel fiber is irreversibly dried at 150 C. to destroy the water-hydrated structure and convert it to a finished fiber form. The finally obtained 3 denier fiber product has a tenacity of about 4.0 grams per denier, an elongation of about 29 percent and a wet yield strength of about 0.90 gram per denier. The copolymer-containing acrylonitrile polymer fiber product is found to have excellent natural stability to heat and light as well as against becoming degraded under the influence of aqueous alkaline media at pH levels as high as 10. It is found to be nearly free of propensity to accumulate charges of static electricity upon handling.

In addition, the graft copolymer-containing sample has good color and hand and is dyeable with all classes of dyestuffs as applied under normal dyeing conditions.

The fiber product dyes well to deep and level shades of coloration with Calcodur Pink ZBL, a direct type of dyestuif (Colour Index Direct Red 75, formerly Colour Index 353) and Sevron Brilliant Red 4G, a basic dye formerely known as Basic Red 4G (Colour Index Basic Red 14).

The dyeing with Calcodur Pink 2BL is performed at the 4 percent level according to conventional procedure in which the fiber sample is maintained for about one hour at the boil in the dye bath which contains the dyestuff in an amount equal to about 4 percent of the weight of the fiber. The dye bath also contains sodium sulfate in an amount equal to about 15 percent of the weight of the fiber and has a bath-to-fiber weight ratio of about 30:1, respectively. After being dyed, the fiber is rinsed thoroughly with water and dried for about 20 minutes at 80 C. The dye-receptivity of the Calcodur Pink 2BL- dyed fiber is then evaluated spectrophotometrically by measuring the amount of monochromatic light having a wave length of about 520 millimicrous from a standard source that is reflected from the dyed sample. A numerical value on an arbitrarily designated scale from to 100 is thereby obtained. This value represents the relative comparison of the amount of light that is reflected from a standard white tile reflector that has a reflectance value of 316 by extrapolation from the 0-100 scale. Lower reflectance values are an indication of better dyereceptivity in the fiber. For example, a reflectance value of about 20 or 25 to 50 or so for acrylonitrile polymer fibers dyed with 4 percent Calcodur Pink 2BL is generally considered by those skilled in the art to be representative of a degree of dye-receptivity that readily meets or exceeds the most rigorous practical requirements and is ordinarily assured of receiving general commercial acceptace and approval. The 4 percent Calcodur Pink 2BL refiactance value of the copolymer-containing fiber prodnet is about 20.

The antistatic properties of the copolymer-containing fiber are then determined by measuring the electrical conductance of the fiber product at various humidities. As is also appreciated by those who are skilled in the art, the basis for such a test is that all fibers have a tendency to generate static electricity upon being handled. Only those that are possessed of suflicient electrical conductance to Volume resistivity (Resistance) (Cross-sectional area) Path length between electrodes to which sample being tested is attached The units of volume resistivity are ohm-cm. /cm.

Prior to being tested, the graft copolymer-containing polyacrylonitrile fiber prepared in the indicated manner is vat dyed in the conventional manner with Cibanone Green BF Dbl. Paste (Colour Index Vat Green No. l). A portion of the vat dyed sample is then subjected to five (5) consecutive N o. 3-A accelerated wash tests in accordance with the American Association of Textile Chemists and Colorists (AATCC) Manual. The actual resistivities of the merely vat dyed sample as well as that of the sample that is both vat dyed and scoured are then determined (after the samples being tested are conditioned for seventy-two hours at the particular temperature and relative humidity conditions involved in each of the tests) by tautly connecting a web-like sample of the yarn between two electrodes, each of which are 9 centimeters long spaced parallel 13 centimeters apart, and across which there is applied a 900 volt direct current potential. For purposes of comparison, the volume resistivities of cotton, wool and an unmodified polyacryonitrile fiber (obtained in the came way as the graft copolymer-containing fiber but without having the polymeric additament incorporated therein) are also tested in the indicated manner along with the graft copolymer-containing fiber in accordance with the present invention.

The results are set forth in the following tabulation which indicates the volume resistivities obtained at various relative humidities (R.H.) at 23 C. of each of the samples tested.

Table 1 VOLUME RESISIIVITIES OF VARIOUS FIBER SAMPLES COMPARED TO POLYACRYLONITRILE FIBERS IM- IREGNATED WITH GRAFT COPOLYMER 0F MONO- MERIC VINYL BENZYL POLYGLYCOL ETIIER AND SODIUM STYRENE SULFONATE ON PVM Volyme Resistivity, ohm-cm. lem.

As is apparent in the foregoing, the graft copolymercontaining sample, even after being severely scoured, has electrical conductance properties much superior to ordinary polyacrylonitrile and only slightly poorer than cotton. At the same time, the physical properties of the copolymercontaining fiber are excellent, being about equal to those of the unmodified polyacrylonitrile fiber.

ILLUSTRATION B The procedure of the first illustration is essentially repeated using the same monomeric vinyl benzyl polyglycol ether to prepare a straight graft copolymer with the monomer from the following charge which is also polymerized in the same way as in the first illustration for 19 hours at about 65 C.:

The resulting product is obtained as a white emulsion that contains about 19.8 percent of dispersed water-insoluble graft copolymer solids. Conversion of the monomer to graft copolymer is found to be greater than 50 percent. The graft copolymer product is comprised of about 20 percent of polymerized units of the monomer on the PVM substrate.

The procedure of the first illustration is repeated to apply the graft copolymer product from 1.5 percent aqueous dispersion to a polyacrylonitrile aquagel fiber in order to obtain a fiber product containing about 10 percent of the graft copolymeric additament incorporated therein. The fiber product has excellent dyeability to deep and level shades of coloration with all classes of dyes excepting basic types. Its 4 percent Calcodur Pink 2BL reflectance value is about 22. The antistatic properties of the fiber are evaluated as in the first example and found to be excellent. As made, the volume resistivities of the graft copolymer-containing fiber product are found to be about 7.0 10 hm-cm. /cm. at 58 percent RH. and about 8.5 10 ohm-cm. cm. at 66 percent R.I-I. After boiling scour, the volume resistivities of the fiber product containing the graft copolymeric additament are found to be about 1.9 10 ohm-cmP/cm. at 58 percent RH. and about 2.3 1O ohm-cm. /cm. at 66 percent RH. Thus, the antistatic characteristics of the fiber product are much better than that of unmodified polyacrylonitrile and compare quite favorably with wool. Its conductivity is not significantly altered by the boiling scour. In addition, as is the case with the fiber product of the first illustration, the stability to heat and light of the graft copolymercontaining fiber product is found to be excellent.

Similar results are also obtained when the foregoing procedure is repeated excepting to prepare the graft copolymer in a reaction mass in which dimethyl sulfoxide is employed as a solvent and azobisisobutyronitrile the catalyst. The graft copolymer prepared in the organic solvent is separated therefrom and prepared in aqueous emulsion for purposes of impregnating the aerylonitrile polymer fiber.

Excellent results commensurate with those set forth in the preceding illustrations may also be obtained when the foregoing is repeated to prepare graft copolymer additives from other N-vinyl-3-morpholinone polymer substrates, such as copolymers of VM with N-vinyl-2-pyrrolidone; N-vinyl-caprolactam; N-vinyl-S-methyl-Z-pyrrolidone; N- vinyl piperidone; and other vinyl lactam monomers; N- vinyl-Z-oxazolidinone; N-vinyl-S-methyl-2-oxazolidinone; Nvinyl-5-ethyl-2-oxazolidinone; N-vinyl-2-oxazinidinone; and other N-vinyl cyclic carbamate monomers; and so forth within the compositional ranges detailed below.

Results similar to those set forth in the foregoing can likewise be obtained when the graft copolymer addita ments are incorportaed in polyacrylonitrile and other aerylonitrile polymer fibers to provide articles in accordance with the present invention by blending the graft copolymer and the fiber-containing aerylonitrile polymer in a spinning composition or dope prior to its extrusion into filamentary products by either wet spinning or dry spinning or dry spinning techniques. In such instances, in cidentally, it may be desirable (in order to secure optimum benefit in the practice of the invention) to employ relatively larger quantities of the graft copolymeric additament than when surface impregnation is performed so that the presence of eflective quantities of the additament at or near the peripheral portion of the article is assured.

The vinyl benzyl polyglycol ether monomers that may onz=orr-@ oni o onionnmw onomonano wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms (i.e., OCH OC H and other -OR groups), alkyl sulfide radicals containing from 1 to about 8 carbon atoms (i.e., -SCH -SC H and other 4R radicals) and halogens of atomic number 17 to 53 (i.e., chlorine, bromine and iodine); m is the number of ethylene glycol groups having an average value from about '2 to about 40; n is the number of proylene glycol groups that includes 0 and has an average value that may be as large as about 20 but is never larger than the value of m, and the sum of the average numerical value of m+n is from about 2 to about 40. In such monomers, the ring-substituted vinyl (CH=CH radical may be ortho, meta or para on the phenyl nucleus relative to the benzyl radical. Likewise, the monomeric product may be obtained in forms of mixtures wherein the vinyl substituent is present on the phenyl nucleus in various positions. The monomeric vinyl benzyl polyglycol ether that is employed may have :a molecular weight between about 200 and 2000, advantageously from about 236 to 1200. These vinyl benzyl polyglycol ether monomers and their preparation are further discussed in the copending application of Stephen C. Stowe for United States Letters Patent having Serial No. 832,443, filed August 10, 1959, entitled Monomeric Alkenyl Benzyl Polyglycol Ethers. The monomeric organic sulfonic acid compounds that may advantageously be mixed with the monomeric vinyl benzyl polyglycol ethers of Formula I for preparation of certain of the graft copolymeric products that may be obtained with benefit in the practice of the invention are monomeric, alkenyl group-containing, organic sulfonic acids or derivatives thereof that are selected from the group of such compounds (including mixtures thereof) consisting of those represented by the formulae:

Y, Rm

0112 (CH2) -S 03X Z (11) (Aromatic organic sulfonic acid compounds) CH =CH-(CH S0 X (HI) (Alkenyl organic sulfouic acid compounds) CHz=C-C ONH-(CH1) n-SOaX (Sulfoalkylacrylate organic sulfonic acid compounds) CHi=(JC ONH(OH) u-SOaX Z (VI) (Allyl taurine homolog compounds) all wherein X is hydrogen, an aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms or an alkali metal ion (including sodium, potassium and lithium); Y is hydrogen, chlorine or bromine; R is methyl or ethyl; Z is hydrogen or methyl; m has a numerical value in Whole number increments from 0 to 2; n has a numerical value of 1 or 2; p is 0 or 1; and r has a numerical value of 1 to 4.

Besides those specifically illustrated herein, other organic sulfonic acids may also be utilized for the preparation of the water-insoluble graft copolymers of the pres ent invention such, by way of illustration, as those which are set forth in the disclosure of United States Letters Patent No. 2,527,300. In addition to the copolymers specifically described in the foregoing examples, other Water-insoluble copolymeric additaments that may advantageously be employed in the practice of the present invention include graft copolymers on the indicated preformed polymer substrates of the various heretofore delineated monomeric polyglycol ethers with such organic sulfonic acids as 2-propene sulfonic acid; sodium paravinylbenzene sulfonate, 2- and/or 3-sulfopropyl acrylate; a-sulfoacrylic acid; sodium vinyl toluene sulfonate; potassium orthochlorostyrene sulfonate; 2-hydroxy-3-sulfopropyl acrylate, sodium salt; sodium 3-allyloxyl-2-hydroxypropane sulfonate; 4-sulfophenyl acrylate, sodium salt; N-allyl imino di-(Z-ethane sulfonic acid); and the like.

Still other organic sulfonic acids that may be employed are as set forth in the following representative (but by no means exhaustive) listing, wherein they are grouped according to the above-designated types.

Aromatic 'alkenyl-containing sulfonic acid compounds (Formula II) Para-styrene sulfonic acid Ortho-styrene sulfonic acid Para-isopropenyl benzene sulfonic acid Para-vinyl benzyl sulfonic acid Ortho-isopropenyl benzyl sulfonic acid Sodium para-styrene sulfonate Potassium ortho-styrene sulfonate Methyl para-styrene sulfonate Ethyl para-vinyl benzyl sulfonate Ortho-vinyl benzyl sulfonic acid Isopropyl ortho-isopropenyl benzene sulfonate n-Butyl ortho-styrene sulfonate Tertiary butyl para-styrene sulfonate 2-chloro-4-vinyl benzene sulfonic acid 4-bromo-2-isopropenyl benzene sulfonic acid 3-viny1 toluene 6-sulfonic acid, sodium salt 2-ethyl-4-vinyl-benzene sulfonic acid 2,3-dichloro-4-vinyl benzene sulfonic acid 2,3,5-tribromo-4-vinyl benzene sulfonic acid 2-chloro-3-vinyl-toluene-6-sulfonic acid 2,3-diethyl-4-vinyl-benzyl sulfonate, sodium salt Alkenyl sulfonic acid compounds (Formula III):

Ethylene sulfonic acid Sodium ethylene sulfonate Potassium ethylene sulfonate Methyl ethylene sulfonate Isopropyl ethylene sulfonate l-propene 3-sulfonic acid l-propene l-sulfonic acid, sodium salt l-propene Z-sulfonic acid, ethyl ester l-butylene 4-sulfonic acid, n-butyl ester l-butylene 3-sulfonic acid Tertiary butylene sulfonic acid Sulfoalkylacrylate compounds (Formula IV):

Sulfomethylacrylate 2-sulfoethylacrylate Sulfomethylemethacrylate, sodium salt Z-sulfoethylemethacrylate, methyl ester 2-sulfoethylmethacrylate, potassium salt Acryloyl taurine and homolog compounds (Formula V):

N-acryloyl taurine N-acryloyl taurine, sodium salt N-methacryloyl taurine, methyl ester N-methacryloyl taurine, potassium salt N-acryloyl taurine, ethyl ester N-arcryloyl-aminomethane sulfonic acid N-methacryloyl-aminomethane sulfonic acid, sodium salt Methyl N-methacryloyl-arninomethane sulfonate Allyl taurine and homolog compounds (Formula VI):

Allyl taurine Allyl taurine, sodium salt Allyl taurine, potassium salt 8 Methallyl taurine Methallyl taurine, methyl ester Methallyl taurine, isopropyl ester N-allyl-aminomethane sulfonic acid Sodium N-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethane sulfonate n-Butyl N-allyl-aminomethane sulfonate The N-vinyl-3-morpholinone polymers that are utilized as preformed substrates in the preparation of the graft copolymeric additaments of the present invention have, as an essential constituent of their polymeric structure, characterizing proportions of the the recurring group As has been indicated, copolymers of N-vinyl-3- morpholinone may also be employed. Thus, copolymers of N-vinyl-3-morpholinone with various homologous alkyl ring-substituted N-vinyl-3-morpholinone monomers may be utilized, such as copolymers of N-vinyl-3-morpholinone, and the like. Copolymers of N-vinyl-3-morpholinone with various N-vinyl lactam polymers, such as N-vinyl pyrrolidone, N-viuyl-pipcridone, N-vinyl caprolactam, N-vinyl-S-methyl-2-pyrrolidone and the like may also be prepared. Advantages are also achieved with copolymers of N-vinyl-3-morpholinone and various of the N-vinyl-Z-oxazolidinone monomers, such as N-vinyl-2- oxazolidinone, N-vinyl-S-methyl-Z-oxazolidinone, N-vinyl- 5-ethyl-2-oxazolidinone, N-vinyl-Z-oxazinidinone, and so forth.

These N-vinyl-3-morpholinone polymers and their preparation are discussed in U.S. Patents 2,952,668, filed April 16, 1958; 2,946,772, filed February 27, 1958; and 2,948,708, filed April 3, 195 8; and in the co-pending application for U.S. patent having Serial Number 692,587, now U.S. 2,987,509, filed October 28, 1957, and entitled N-Vinyl-3-Morpholin0ne Compounds.

Advantageously, the N-vinyl-3-morpholinone polymer that is used in the manufacture of the graft copolymer product has a Fikentscher K-value between about 5-10 and about and, more advantageously, between about 20-30 and 60.

Beneficially, as mentioned, the N-vinyl-3-morpholinone polymer that is utilized is a water-soluble material. In cases Where N-vinyl-B-morpholinone copolymers are employed that tend to water-insolubility with decreasing proportions of N-vinyl-3-morpholinone in the copolymer molecule (as is the case with copolymers of N-vinyl-3- morpholinone and N-vinyLS-methyl-Z-oxazolidinone), it is generally most desirable for the copolymer to contain at least about 40 weight percent of the N-vinyl-3-morpho linone polymerized therein. This avoids working with a product that may have a cloud (or precipitation) point in water or other aqueous solution beneath the boil.

The graft copolymers of the present invention may generally be prepared by methods of polymerization, such as those which have been demonstrated in the foregoing illustrative examples, that employ such polymerization catalysts as persulfates, organic and inorganic peroxide and azo type materials (such as azobisisobutyronitrile) in quantities that are conventional for such uses. The graft copolymers may oftentimes be prepared by polymerizing the monomeric constituent onto the preformed polymer substrate under the influence of high energy irradiation such as by means of X-rays and the like. The graft copolymers may be prepared in both aqueous and organic solvent vehicles using temperatures for the desired polymerization that may vary from about room temperature to the boiling point of the polymerization mixture. It is ordinarily satisfactory to conduct the reaction at a temperature of about 50 to 80 or 100 C. Usually, depending on the specific factors that may be involved, the graft copolymerization may be accomplished satisfactorily within a time period of about to 60 hours.

The compositions of the graft copolymeric additaments that are employed can vary within relatively Wide limits. The content of the monomeric constituent, whether it is the monomeric vinyl benzyl polyglycol ether being individually employed or in combination with the monomeric organic sulfonic acid compounds, may advantageously be between about 20 and 80 percent by weight of a graft copolymer, with the preformed polymer substrate consisting of the remaining 80 to 20 percent of the polymeric product. In many cases, especially to secure optimum dye-receptivity, nearly equivalent or about commensurate proportions of the graft copolymerized monomeric constituent and the preformed polymer substrate upon which it is graft copolymerized may be employed for the preparation of the graft copolymeric additaments. When the monomeric vinyl benzyl polyglycol ether is employed in mixtures with monomeric organic sulfonic acid compounds for prepartion of the graft copolymer products, either of the diverse type of monomers may be present in the mixture in proportions of from about 10 to 90, advantageously from about 30 to 70 mole percent of either monomer. Thus, a mixture of a vinyl benzyl polyglycol ether monomer with an organic sulfonic acid monomer can advantageously contain from 10 to 90 mole percent of the former with the balance of the mono rneric mixture consisting of the monomeric organic sulfonic acid compound.

The polymerization system that is employed for the preparation of the graft copolymers used in the present invention may consist of as much as 50 weight percent of the monomers to be polymerized in the aqueous or other medium. The amount of polymerizable constituents that are provided in the copolymerization system may be influenced somewhat by the manner in which it is intended to incorporate the product in the synthetic polymer compositions in order to provide the compositions of the invention.

If, for example, it is intended to incorporate the graft copolymer products by blending into a fiber-forming composition prior to its fabrication into shaped articles, the graft copolymerization system may, if desired, contain about equal proportions by weight of the charged polymerizable constituents and the polymerization medium which preferably is miscible with and tolerable in the spinning solution solvent being used. In such cases, the graft copolymer product may ordinarily be obtained as an easily dispersed gel that, after being dried and isolated from unreacted monomer, may readily be directly incorporated in the fiber-forming composition.

If the incorporation of the graft copolymeric additament in a fiber-forming composition is to be achieved by impregnation therewith of an already-formed shaped article of the composition, it may be desirable to effect the polymerization so as to directly form the polymerization system as a suitable applicating emulsion or suspension of the graft copolymeric product, or as a solution when sufiiciently hydrophilic polyglycol constituents are present in the monomeric vinyl benzyl polyglycol ether employed. For such purposes, the polymerization system may be prepared to contain as little as S or 10 percent by weight of the polymerizable monomeric and polymeric ingredients. Preferably, if the graft copolymer is Waterinsoluble, such a polymerization may be conducted under the influence of vigorous agitation to facilitate preparation of an emulsified or thoroughly dispersed product. 70

preparing the graft copolymeric additaments that are 75 10 employed in the present invention may be especially appropriate when they are intended to be applied to acrylomtrile polymer fibers and the like that are derived from aquagels in the course of their manufacture, such as the acrylonitrile polymer fibers that are wet spun from aqueous saline solutions of the fiber-forming polymer.

In such instances, as has been demonstrated, the emulsified, graft copolymeric additaments may be impregnated into the fiber while it is in a swollen or gel condition, as an acrylonitrile polymer fiber in an aquagel condition, in order to obtain the desired copolymer-containing product. A dissolved, water-soluble product may be similarly impregnated.

In this connection, when it is desired to blend the graft copolymeric additament in a synthetic polymer fiberforming solution prior to its extrusion, such as an aqueous saline acrylonitrile polymer solution, a water-insoluble graft copolymer may be physically reduced by comminutron to a sufficiently fine state to permit its dispersion in spinnable condition throughout the blended spinning solution in the solvent if it is otherwise insoluble in the solvent. While this may be accomplished by diverse techniques, it is generally advantageous to comminute the graft copolymer in the presence of the non-dissolving solvent, such as an aqueous saline polyacrylonitrile solvent, to form a stable suspension that may be more conveniently blended with the spinning solution of the synthetic polymer, such as an aqueous saline acrylonitrile polymer spinmng solution. Thus, if the aqueous saline polyacryonitrile solvent that is being employed is an aqueous solutron of zinc chloride, or its equivalent that contains at least about 55 percent and preferably about 60 percent by weight of dissolved zinc chloride, it may be advantageous to comminute a water-insoluble graft copolymeric additament while it is in a mixture with the saline solvent solution that contains between about 5 and 10 percent by weight of the copolymer. Analogous procedures may be employed when other solvents are involved. Ball or rod mills or other attrition apparatus may be employed beneficially for the comminution. It is generally beneficial under such circumstances to avoid the use of balls or rods that are made of metal since they may contaminate the product, especially when aqueous saline solvents are utilized. Porcelain or other ceramic parts may usually be employed with advantage. A stable suspension of a water-insoluble graft copolymeric additament in the acrylonitrile polymer solvent that is suitable for blending in the spinning solution of the acrylonitrile polymer to provide a spinnable composition may usually be obtained by milling the mixture of graft copolymeric additament and solvent for an extended period that may exceed hours. The suspension that is thereby obtained may then be directly blended in the proper proportions with the acrylonitrile polymer spinning solution to provide a composition in accordance with the present invention.

If desired, the graft copolymer-containing acrylonitrile polymer compositions may comprise as much as 20 or more percent by weight of the graft copolymeric additament, based on the weight of the composition. Usually, however, suitable properties and characteristics and better fiber-forming properties in a given composition may be achieved when lesser proportions of the graft copolymeric additament are incorporated therein. An appreciable improvement in dye-receptivity, antistatic prop erties and stability may frequently be obtained when a quantity of the graft copolymeric additament that is as small as 2 (and even as low as 1 or less) percent by weight is employed. Advantageously, an amount between about 4 and 15 percent by weight of the copolymeric additament may thus be utilized in the composition. Greater advantages may often accrue when the amount of the copolymeric additament that is incorporated in the composition is in the neighborhood of -10 percent by weight, based on the weight of the composition.

As has been indicated, the graft copolymeric additaments may be incorporated in the acrylonitrile polymer compositions according to various techniques. Thus, for example, the copolymeric additament and the acrylonitrile polymer may be directly blended in order to provide the composition which, incidentally, may be used for any desired fabrication purpose in addition to fiber-forming and the like. Beneficially, the polymers may be comminuted, either separately or in combination, before being intimately blended together by mechanical or other means. The blended polymers may be prepared into suitable fiberforming systems by dissolving or otherwise dispersing them in a suitable liquid medium. Or, the compositions may be provided in fiber-forming system by sequentially dispersing the polymers in any desired order in a suitable medium, as by incorporating the copolymeric additament in a prepared acrylonitrile polymer spinning solution, dope, or the like.

As is evident from the exemplifying illustrations heretofore included, a highly advantageous technique for providing the compositions, particularly when acrylonitrile polymer fiber products are involved, is to apply or impregnate the graft copolymeric additament from an aqueous dispersion thereof to a shaped acrylonitrile polymer article that is in an aquagel condition in a known manner. Thus, an acrylonitrile polymer filamentary article that has been spun from an aqueous saline spinning solution may be conveniently passed, after its coagulation and while it is in an aquagel condition, through a water bath containing the dissolved graft copolymeric additament in order to impregnate the filament with the graft copolymer and provide a composition and an article in accordance with the invention. In addition, in situ polymerization techniques may also be relied upon to provide the graft copolymeric additament in the acrylonitrile polymers in either fabricated or unfabrieated form.

The compositions of the invention may advantageously be utilized in or with fiber-forming systems of any desired type in order to provide fibers and the like according to procedures and techniques that are conventionally employed for such purposes in the preparation of fibers and such related shaped articles as filaments, strands, yarns, tows, threads, cords and other funicular structures, ribbons, tapes, films, foils, sheets and the like which may be manufactured from synthetic polymeric materials. It is frequently desirable to employ concentrated solutions of salts or mixtures of salts as the dispersing or dissolving media for such purposes. Such solutions may, as has been indicated, contain at least about 55 percent by weight, based on the weight of the solution, of zinc chloride or other known saline solvents for the polymer. Acrylonitrile polymer fiber products that are spun from saline fiber-forming systems may, by way of further illustration, be coagulated in more dilute saline solutions of a like or similar nature and may then be processed after coagulation according to conventional techniques of washing, stretching, drying, finishing and the like with the modification of the present invention being accomplished prior or subsequent to the spinning as may be desired and suitable in particular instances.

The acrylonitrile polymer fiber products in accordance with the present invention (one of which is schematically illustrated in the sole FIGURE of the accompanying drawing) have excellent physical properties and other desirable characteristics for a textile material and have a high capacity for and are readily and satisfactorily dyeable to deep and level shades with any of a wide variety of dyestuffs. For example, they may be easily and suceessfully dyed according to conventional procedures using acid, vat, acetate, direct, naphthol and sulfur dyes.

Such dyestuffs, by way of didactic illustration, as Calcocid Alizarine Violet (Colour Index 61,710, formerly Colour Index 1080), Sulfanthrene Red 3B (Colour In-. dex Vat Violet 2), Amacel Scarlet GB (Colour Index Direct Red 1 also known as Amacel Scarlet BS, and having American Prototype Number 244), Calcodur Pink 2BL (Colour Index 353, also more recently, Colour Index Direct Red 75), Naphthol ASMX (Colour Index 35,527), Fast Red TRN Salt (Colour Index AZoic Diazo Component 11), and Immedial Bordeaux G (Colour Index Sulfur Brown 12) may advantageously be employed for such purposes.

Other dyestuffs, by way of further illustration, that may be utilized beneficially on the graft copolymer-containing acrylonitrile polymer blended fiber products of the invention include such direct cotton dyes as Chlorantine Fast Green SBLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B (Colour Index Direct Red 81), Pontamine Green GX Conc. 125 percent (Colour Index Direct Green 6), Calcomine Black EXN Conc. (Colour Index Direct Black 38), Niagara Blue NR (Colour Index Direct Blue 151) and Erie Fast Scarlet 4BA (Colour Index Direct Red 24); such acid dyes as Anthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2R (Colour Index Acid Orange 51), Sulfonine Yellow 2G (Colour Index Acid Yellow 40), Xylene Milling Black 23 (Colour Index Acid Black 26A), Xylene Milling Blue FF (Colour Index Acid Blue 61), Xylene Fast Rubine 3GP PAT (Colour Index Acid Red 57), Calcocid Navy Blue R Cone. (Colour Index Acid Blue 120), Calcocid Fast Blue BL (Colour Index Fast Blue 59), Calcocid Milling Red 3R (Colour Index Acid Red 151), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Amacid Azo Yellow G Extra (Colour Index Acid Yellow 63); such mordant-acid dyes as Alizarine Light Green GS (Colour Index Acid Green 25); such basic dyes as Brilliant Green Crystals (Colour Index Basic Green 1), and Rhodamine B Extra S (Colour Index Vat Blue 35); such vat dyestuffs as Midland Vat Blue R Powder (Colour Index Vat Blue 35), Sulfanthrene Brown G Paste (Colour Index Vat Brown 5), Sulfanthrene Blue 2B Dbl. paste (Colour Index Vat Blue 5), and Sulfanthrene Red 3B paste (Colour Index Vat Violet 2); various soluble vat dyestuffs; such acetate dyes as Celliton Fast Brown 3RA Extra CF (Colour Index Dispersed Orange 5), Celliton Fast Rubine BA CF (Colour Index Dispersed Red 13), Artisil Direct Red 38F and Celanthrene Red 3BN Cone. (both Colour Index Dispersed Red 15), Celanthrene Pure Blue BRS 400 percent (Colour Index Dispersed Blue 1) and Acetamine Yellow N (Colour Index Dispersed Yellow 32); B-Naphthol 2-chloro-4-nitroaniline, an azoic dye; such sulfur dyes as Katigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) and Indo Carbon CLGS (Colour Index Sulf. Blue 6); and various premetallized dyestuffs.

The dyed products are generally lightfast and stable to heat and are well imbued with a good resistance to crocking. In addition, the dyed products exhibit good washfastness and retain the dye-assisting graft copolymeric additament in a substantially permanent manner, despite repeated exposure and subjection to washing, laundering and dry cleaning treatments.

What is claimed is:

1. Graft copolymer of between about 20 and about weight percent of (a) a monomeric vinyl benzyl polyglycol ether of the general formula:

OHz=CHOCHz CH2CII2)m(OCHCHsCH:) no (I) wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; in has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus n is from about 2 to about 40; and (b) from about 80 to about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-B-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-Vinyl- 3-morpholinone.

2. The graft copolymer of claim 1, containing in the polymer molecule, in polymerized form, between about 30 and about 50 weight percent of said monomer as graft copolymerized substituents on said N-vinyl-3-morpholinone polymer.

3. The graft copolymer of claim 1, wherein said N-vinyl 3 morpholinone polymer is poly-N-vinyl-3- morpholinone.

4. Graft copolymer of between about 20 and about 80 weight percent of (a) a mixture of monomers consisting of from about 10 to about 90 mole percent of 1) a monomeric vinyl benzyl polyglycol ether of the formula:

wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; m has an average value from about 2 to about 40; n has an average value of from to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus n is fromabout 2 to about 40; and (2) from about 90 to about mole percent of an alkenyl group-containing organic sulfonic acid compound selected from the group consisting of those represented by the formulae:

Yr Rm CH2=C (CH2) r-SOsX (II) oH2=0]1-(0Hi)m-s 03X (III) oH2=o-0 o O-(CHz) 11-8 03X i av) CH2=OC ONE-(CH2) vs 0 3X CH =O-CHz-NH(CH2) ns 03X i (VI) all wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to l; and r is an integer from 1 to 4; and (b) from about 80 to about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolyrnerizable with N-vinyl-3-morphilinone.

5. Method for the preparation of a graft copolymer which comprises polymerizing between about 20 and about 80 weight percent, based on resulting graft copolymer weight, of a monomeric vinyl benzyl polyglycol ether having the formula:

onz=on -om(oonzonnmwonomom)He (I) wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing firom 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; m has an average value from about 2 to about 40; n has an average value of from O to about 20 with the limitation that the value of n is always less than that of m and the sum total of m plus n is from about 2 to about 40; with between about and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-S-morpholinone and up to weight percent of another polymerized N-vinyl beterocyclic compound which compound is copolymerizable with N-vinyl- 3-morpholinone.

6. Method for the preparation of a graft copolymer which comprises polymerizing between about 20 and about 80 weight percent, based on resulting graft copolymer weight, of (a) a mixture of monomers consisting of from about 10 to about 90 mole percent of (1) a monomeric vinyl benzyl polyglycol ether of the formula:

wherein G is selected firom the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; aikyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; m has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus 11 is from about 2 to about 40; and (2) from about 90 to 10 mole percent of an alkenyl groupcontaining organic sulfonic acid compound selected from the group consisting of those having the formulae:

Yr- Rm CH2=C (ours-soar (II) CHFCH-(CH2) -SOgX (III) 011i=c :-0 o 0- 011i) n-SOaX Z (IV) CH2=C|1-C ONE-(CH2) Peon:

i W) all wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; with (b) between about 80 and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone.

7. Composition comprising a major proportion of at least about 80 weight percent, based on composition weight, of (A) a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile, and (B) a minor proportion of up to about 20 Weight percent, based on composition weight, of a graft copolymer of (a) between about 20 and about 80 weight percent of a monomeric vinyl benzyl polyglycol ether having the formula:

mama-Q0112 oonzonnmmonon om)HG (I) wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; in has an average value from about 2 to about 40; n has an average value of from to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus n is from about 2 to about 40; and (b), between about 80 and about 20 weight percent of a polymerized monocthylenically unsaturated monomeric material containing at least about weight percent of polymerized N-vinyl-S-morpholinone and up to 90 weight percent of another polymerized N vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone.

8. The composition of claim 7 containing between about 4 and about weight percent, based on composition weight, of said graft copolymer.

9. The composition of claim 7, wherein the graft copolymer is a monomer of said Formula I wherein m is 2 and n is 0 and poly-N-vinyl-3-morpholinone.

10. The composition of claim 7, wherein the graft copolymer is a monomer of said Formula I wherein m is 15 and n is 0 and poly-N-vinyl-3-morpholinone.

11. The composition of claim 7, wherein the graft copolymer is a monomer of said Formula I wherein m is and n is 2-poly-N-vinyl-3-morpholinone.

12. The composition of claim 7, wherein the acrylonitrile polymer is polyacrylonitrile.

13. The composition of claim 7, dispersed in a solvent for polyacrylonitrile.

14. A filamentary shaped article having the composition set forth in claim 7.

15. Composition comprising a major proportion of at least about 80 weight percent, based on composition weight, of (A) a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile, and (B) a minor proportion of up to about 20 weight percent, based on composition weight, of a graft copolymer of (a) from about 20 to about 80 Weight percent of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of a monomeric vinyl benzyl polyglycol ether of the formula:

wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; m has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus 11 is from about 2 to about 40; and (2) from about 90 to about 10 mole percent of an alkenyl groupcontaining organic sulfonic acid compound selected from the group consisting of those having the formulae:

all wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, in is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b), between about and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to weight percent of another N-vinyl heterocyclic compound copolymerizable with N-vinyl-3-morpholinone.

16. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, linear, hydrophobic polymer composition which comprises mixing together a minor proportion of up to about 20 weight percent, based on composition weight, of (B) a graft copolymer of (a) between about 20 and about 80 weight percent of a monomeric vinyl benzyl polyglycol ether of the formula:

oH2=oH--o112 oomom)m 0 ononaorn) no (I) wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; 121 has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus 11 is from about 2 to about 40; and (1)), between about 80 and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-S-morpholinone; with (A) at least about 80 weight percent, based on composition weight, of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile.

17. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, linear, hydrophobic polymer composition which comprises mixing together a minor proportion of up to about 20 weight percent, based on composition weight of (B) a graft copolymer of (a) between about 20 and about 80 weight percent of a mixture of monomers consisting of 1) from about 10 to about 90 mole percent of a monomeric vinyl benzyl polyglycol ether of the formula:

om=on-onno ouzortnmto onornom) no wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; in has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus 11 is from about 2 to about 40; and (2) from about 90 to about 10 mole percent of an alkenyl groupcontaining organic sulfonic acid compound selected from the group consisting of those having the formulae:

Y, Rm

all wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b), between about 80 and 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone; with (A) at least about 80 weight percent, based on composition weight, of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile.

18. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, linear hydrophobic polymer composition which comprises immersing an aquagel of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile in the form of a shaped article into a dispersion of a graft copolymer of (a) between about 20 and about 80 weight percent of a monomeric vinyl benzyl polyglycol ether of the formula:

OHz=CH-OH1 (001120119111 (0 CH CH CH2) AG (1) wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 3 m has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus it is from about 2 to about 40; and (b), between about 80 and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound, which compound is copolymerizable with N-vinyl-3-morpholinone until between about 2 to about 20 weight percent of said graft copolymer, based on resulting dry composition weight, is incorporated in said aquagel; and drying said graft copolymer-containing aquagel to convert it from the aquagel condition to a finished shaped article form.

19. Method for the preparation of a dye-receptive, antistatic, Stable to light and heat, synthetic, linear, hydrophobic polymer composition which comprises immersing an aquagel of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile in the form of a shaped article into a dispersion of a graft copolymer of (a) from about 20 and about 80 weight percent of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of a monomeric vinyl benzyl polyglycol ether of the formula:

OHZ=CHOCHKO omornmoonornonmo wherein G is selected from the group consisting of alkoxy radicals containing from 1 to about 8 carbon atoms; alkyl sulfide radicals containing from 1 to about 8 carbon atoms and halogens of atomic number 17 to 53; in has an average value from about 2 to about 40; n has an average value of from 0 to about 20 with the limitation that the value of n is always less than that of m and the sum total of in plus n is from about 2 to about 40; and (2) from about 90 to about 10 mole percent of an alkenyl group-containing organic sulfonic acid compound selected from the group consisting of those having the formulae:

all wherein X is selected from the group consisting of hydrogen, aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl, m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; r is an integer from 1 to 4; and (12), between about and about 20 weight percent of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to weight percent of another polymerized tN-vinyl heterocyclic compound, which compound is copolymerizable with N-vinyl-3-morpholinone until between about 2 and about 20 weight percent of said graft copolymer, based on resulting dry composition weight basis, is incorporated in said aquagel; and drying said graft copolymer-containing aquagel to convert it from the aquagel condition to a finished shaped article form.

References Cited in the file of this patent UNITED STATES PATENTS 

1. GRAFT COPOLYMER OF BETWEEN ABOUT 20 AND ABOUT 80 WEIGHT PERCENT OF (A) A MONOMERIC VINYL BENZYL POLYGLYCOL ETHER OF THE GENERAL FORMULA: 